Milani Roberto, Houbenov Nikolay, Fernandez-Palacio Francisco, Cavallo Gabriella, Luzio Alessandro, Haataja Johannes, Giancane Gabriele, Saccone Marco, Priimagi Arri, Metrangolo Pierangelo, Ikkala Olli
VTT Technical Research Centre of Finland Ltd., 02044 VTT Espoo, Finland.
Department of Applied Physics, HYBER Centre of Excellence, Aalto University, 02150 Espoo, Finland.
Chem. 2017 Mar 9;2(3):417-426. doi: 10.1016/j.chempr.2017.02.003.
Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions. Here, we use halogen bonding as a supramolecular tool that directs the hierarchical self-assembly of low-molecular-weight perfluorinated molecules and diblock copolymers. Microphase separation results in a lamellar-within-cylindrical arrangement and promotes upright cylindrical alignment in films upon rapid casting and without further annealing. Such cylindrical domains with internal lamellar self-assemblies can be cleaved by solvent treatment of bulk films, resulting in separated and segmented cylindrical micelles stabilized by halogen-bond-based supramolecular crosslinks. These features, alongside the reversible nature of halogen bonding, provide a robust modular approach for nanofabrication.
将嵌段共聚物自组装成化学性质不同的区域的明确、有序排列是制备定制纳米结构的可靠策略。微相分离源于该系统，它使不同嵌段之间的排斥相互作用最小化，并使相似嵌段之间的吸引相互作用最大化。超分子方法也通过引入通过非共价相互作用与一个嵌段特异性结合的小分子添加剂实现了这种分离。在这里，我们使用卤素键作为一种超分子工具，来指导低分子量全氟分子和二嵌段共聚物的分级自组装。微相分离导致圆柱状内部呈层状排列，并在快速浇铸且无需进一步退火的情况下促进薄膜中圆柱状的垂直排列。这种具有内部层状自组装的圆柱状区域可以通过对本体薄膜进行溶剂处理来裂解，从而产生由基于卤素键的超分子交联稳定的分离且分段的圆柱状胶束。这些特性，连同卤素键的可逆性质，为纳米制造提供了一种强大的模块化方法。
